Heteroleptic Cu(I) complexes with 1,10-octachlorophenanthroline (OCP) [Cu₂(OCP)₂×₂] (X = Br (1), I (2)) were prepared and characterized by X-ray diffractometry (XRD) and thermogravimetric analysis (TGA). In the structures of 1 and 2, there are Cl•••Br and Cl•••I non-covalent interactions which can be regarded as halogen bonding (XB); according to DFT calculations, their energies are up to 2.1 kcal/mol.